U.S. patent number 4,636,322 [Application Number 06/795,023] was granted by the patent office on 1987-01-13 for lubricating oil dispersant and viton seal additives.
This patent grant is currently assigned to Texaco Inc.. Invention is credited to Theodore E. Nalesnik.
United States Patent |
4,636,322 |
Nalesnik |
January 13, 1987 |
Lubricating oil dispersant and viton seal additives
Abstract
A lubricating oil composition having improved dispersancy and
viton seal compatibility. the dispersant being prepared by coupling
partly glycolated succinimides with an aldehyde and a phenol.
Inventors: |
Nalesnik; Theodore E. (Beacon,
NY) |
Assignee: |
Texaco Inc. (White Plains,
NY)
|
Family
ID: |
8196242 |
Appl.
No.: |
06/795,023 |
Filed: |
November 4, 1985 |
Current U.S.
Class: |
508/292;
548/520 |
Current CPC
Class: |
C10M
159/16 (20130101); C10M 133/56 (20130101); C10M
2217/06 (20130101); C10M 2215/04 (20130101); C10N
2040/251 (20200501); C10N 2040/28 (20130101); C10M
2215/26 (20130101); C10M 2215/28 (20130101); C10M
2217/046 (20130101); C10N 2040/25 (20130101); C10N
2040/255 (20200501); C10M 2215/086 (20130101); C10N
2070/02 (20200501) |
Current International
Class: |
C10M
133/00 (20060101); C10M 133/56 (20060101); C10M
159/00 (20060101); C10M 159/16 (20060101); C10M
107/44 (); C10M 145/20 (); C10M 149/16 () |
Field of
Search: |
;252/52A,51.5A,56D,56R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Dixon, Jr.; William R.
Assistant Examiner: McAvoy; Ellen M.
Attorney, Agent or Firm: Kulason; Robert A. O'Loughlin;
James J. Mallare; Vincent A.
Claims
I claim:
1. A lubricating oil composition comprising a major portion of a
lubricating oil and a minor dispersant amount of a reaction product
prepared by the process which comprises:
(a) reacting a polyamine with an alkenyl succinic acid anhydride to
form a bis-alkenyl succinimide;
(b) acylating said bis-alkenyl-succinimide with glycolic acid to
form a partially glycolated bis-alkenyl succinimide;
(c) adding an excess of an aldehyde to said partially glycolated
bis-alkenyl succinimide to form an iminium salt of the glycolated
bis-alkenyl succinimide;
(d) adding a phenol to said iminium salt, thereby forming a Mannich
phenol coupled glycamide bis-alkenyl succinimide; and
(e) recovering said Mannich phenol coupled glycamide bis-alkenyl
succinimide.
2. The lubricating composition of claim 1, wherein from about 0.5
to about 3.0 equivalents of glycolic acid are added per mole of
polyethylene amine.
3. The lubricating composition of claim 2, wherein about 0.7
equivalents of glycolic acid are added per mole of polyethylene
amine.
4. The lubricating composition of claim 2, wherein about 2.7
equivalents of glycolic acid are added per mole of polyethylene
amine.
5. The lubricating oil composition of claim 1, wherein said
polyamine is represented by the formula ##STR5## where R' is H or a
hydrocarbon selected from the group consisting of alkyl, aralkyl,
cycloalkyl, aryl, alkaryl, alkenyl and alkynyl group; R" is a
hydrocarbon selected from the same group as R' except that R"
contains one less H; a is an integer of about 3 to about 8; and n
is 0 or 1.
6. The lubricating oil composition of claim 5, wherein said amine
is selected from the group consisting of triethylenetetramine,
tetraethylene-pentamine and pentaethylenehexamine.
7. The lubricating oil composition of claim 6, wherein said amine
is tetraethylenepentamine.
8. The lubricating oil composition of claim 6, wherein said amine
is pentaethylenehexamine.
9. The lubricating oil composition of claim 6, wherein said amine
is triethylenetetramine.
10. The lubricating oil composition of claim 1, wherein oxalic acid
is substituted for said glycolic acid.
11. The lubricating oil composition of claim 1, wherein said
aldehyde is selected from the group consisting of formaldehyde,
paraformaldehyde, ethanal, propanal and butanal.
12. The lubricating oil composition of claim 1, wherein said
aldehyde is paraformaldehyde.
13. The lubricating oil composition of claim 1, wherein said phenol
is selected from the group consisting of phenol, bisphenol A,
resorcinol, mono-nonyl phenol, and beta-naphthol.
14. The lubricating oil composition of claim 13, wherein said
phenol is phenol.
15. The lubricating oil composition of claim 13, wherein said
phenol is nonyl phenol.
16. The lubricating oil composition of claim 1, wherein said
reaction product is an acylated Mannich phenol coupled glycamide
bis-alkenyl succinimide ##STR6## where R is polyisobutylene and x
is an integer of 1 to 6.
17. A lubricating oil composition comprising a major portion of a
lubricating oil and minor dispersant amount of a reaction product
prepared by the process which comprises:
(a) reacting an alkenyl succinic acid anhydride with a polyamine
##STR7## where R' is H or a hydrocarbon selected from the group
consisting of alkyl, aralkyl, cycloalkyl, aryl, alkaryl, alkenyl
and alkynyl group; R" is a hydrocarbon selected from the same group
as R' except that R" contains one less H; a is an integer of about
3 to about 8 and n is 0 or 1, to form a bis-alkenyl succinimide
##STR8## where R is polyisobutylene and x is an integer of 1 to 6;
(b) acylating said bis-alkenyl-succinimide with a carboxylic acid
to form a partially glycolated bis-alkenyl succinimide ##STR9## (c)
adding an excess of formaldehyde to said partially glycolated
bis-alkenyl succinimide to form an iminium salt of the glycolated
bis-alkenyl succinimide ##STR10## (d) adding a phenol to said
iminium salt, thereby forming a Mannich base phenol coupled
glycamide bis-alkenyl succinimide ##STR11## and (e) recovering said
acylated Mannich phenol coupled glycamide bis-alkenyl succinimide.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
Internal combustion engines operate under a wide range of
temperatures including low temperature stop-and-go service as well
as high temperature conditions produced by continuous high speed
driving. Stop-and-go driving, particularly during cold, damp
weather conditions, leads to the formation of a sludge in the
crankcase and in the oil passages of a gasoline or a diesel engine.
This sludge seriously limits the ability of the crankcase oil to
effectively lubricate the engine. In addition, the sludge with its
entrapped water tends to contribute to rust formation in the
engine. These problems tend to be aggravated by the manufacturer's
lubrication service recommendations which specify extended oil
drain intervals.
It is known to employ nitrogen containing dispersants and/or
detergents in the formulation of crankcase lubricating oil
compositions. Many of the known dispersant/detergent compounds are
based on the reaction of an alkenylsuccinic acid or anhydride with
an amine or polyamine to produce an alkylsuccinimide or an
alkenylsuccinamic acid as determined by selected conditions of
reaction.
It is also known to chlorinate alkenylsuccinic acid or anhydride
prior to the reaction with an amine or polyamine in order to
produce a reaction product in which a portion of the amine or
polyamine is attached directly to the alkenyl radical of the
alkenylsuccinic acid or anhydride. The thrust of many of these
processes is to produce a product having a relatively high level of
nitrogen in order to provide improved dispersancy in a crankcase
lubricating oil composition.
With the introduction of four cylinder internal combustion engines
which must operate at relatively higher engine speeds or RPM's than
conventional 6- and 8-cylinder engines in order to produce the
required torque output, it has become increasingly difficult to
provide a satisfactory dispersant lubricating oil composition.
Another problem facing the lubricant manufacturer is that of seal
deterioration in the engine. All internal combustion engines use
elastomer seals, such as Vitron seals, in their assembly. Over
time, these seals are susceptible to serious deterioration caused
by the lubricating oil composition. A lubricating oil composition
that degrades the elastomer seals in an engine is unacceptable to
engine manufacturers and has limited value.
It is an object of this invention to provide a novel lubricating
oil additive.
Another object is to provide a novel lubricating oil composition
which does not degrade elastomer seals in internal combustion
engines.
A still further object is to provide a lubricating oil composition
which can withstand the stresses imposed by modern internal
combustion engines.
2. Disclosure Statement
U.S. Pat. Nos. 3,172,892 and 4,048,080 disclose alkenylsuccinimides
formed from the reaction of an alkenylsuccinic anhydride and an
alkylene polyamine and their use as dispersants in a lubricating
oil composition.
U.S. Pat. No. 2,568,876 discloses reaction products prepared by
reacting a monocarboxylic acid with a polyalkylene polyamine
followed by a reaction of the intermediate product with an alkenyl
succinic anhydride.
U.S. Pat. No. 3,216,936 discloses a process for preparing an
aliphatic amine lubricant additive which involves reacting an
alkylene amine, a polymer substituted succinic acid and an
aliphatic monocarboxylic acid.
U.S. Pat. No. 3,131,150 discloses lubricating oil compositions
containing dispersant-detergent mono- and di-alkyl-succinimides or
bis(alkenylsuccinimides).
Netherlands Pat. No. 7,509,289 discloses the reaction product of an
alkenylsuccinic anhydride and an aminoalcohol, namely a
tris(hydroxymethyl)-aminomethane.
U.S. patent application, Ser. No. 334,774, filed on Dec. 28, 1981,
discloses a hydrocarbyl-substituted succinimide dispersant having a
secondary hydroxy-substituted diamine or polyamine segment and a
lubricating oil composition containing same.
U.S. Pat. No. 4,338,205 discloses alkenyl succinimide and borated
alkenyl succinimide dispersants for a lubricating oil with impaired
diesel dispersancy in which the dispersant is treated with an
oil-soluble strong acid.
The disclosures of U.S. Pat. Nos. 3,172,892 and 4,048,080 and of
application Ser. No. 334,774 are incorporated herein by
reference.
SUMMARY OF THE INVENTION
The present invention provides a novel additive which improves the
dispersancy and viton seal compatibility of a lubricating oil. The
lubricating oil composition comprises a major portion of a
lubricating oil and a minor dispersant amount of a reaction product
prepared by the process which comprises:
(a) reacting a polyethylene amine with an alkenyl succinic acid
anhydride to form a bis-alkenyl succinimide;
(b) acylating said bis-alkenyl-succinimide with glycolic acid to
form a partially glycolated bis-alkenyl succinimide;
(c) adding an excess of a formaldehyde to said partially glycolated
bis-alkenyl succinimide to form an iminium salt of the glycolated
bis-alkenyl succinimide;
(d) adding a phenol to said iminium salt, thereby forming an
acylated Mannich phenol coupled glycamide bis-alkenyl succinimide;
and
(e) recovering said acylated Mannich phenol coupled glycamide
bis-alkenyl succinimide.
DESCRIPTION OF THE INVENTION
The charge polyamine compositions which may be employed in practice
of the process of this invention according to certain of its
aspects may include primary amines or secondary amines. The amines
may typically be characterized by the formula ##STR1##
In these formulae, a may be an integer of 3 to 8, preferably about
5; and n may be 0 or 1.
In the above compound, R' may be hydrogen or a hydrocarbon group
selected from the group consisting of alkyl, aralkyl, cycloalkyl,
aryl, alkaryl, alkenyl, and alkynyl including such radicals when
inertly substituted. When R' is alkyl, it may typically be methyl,
ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, sec-butyl, amyl,
octyl, decyl, octadecyl, etc. When R' is aralkyl, it may typically
be benzyl, beta-phenylethyl, etc. When R' is cycloalkyl, it may
typically be cyclohexyl, cycloheptyl, cyclooctyl,
2-methylcyclo-heptyl, 3-butylcyclohexyl, 3-methylcyclohexyl, etc.
When R' is aryl, it may typically be phenyl, naphthyl, etc. When R'
is alkaryl, it may typically be tolyl, xylyl, etc. When R' is
alkenyl, it may typically be allyl, 1-butenyl, etc. When R' is
alkynyl, it may typically be propynyl, butynyl, etc. R' may be
inertly substituted i.e. it may bear a non-reactive substituent
such as alkyl, aryl, cycloalkyl, ether, halogen, nitro, etc.
Typically inertly substituted R' groups may include 3-chloropropyl,
2-ethoxyethyl, carboethoxymethyl, 4-methyl, cyclohexyl,
p-chlorophenyl, p-chlorobenzyl, 3-chloro-5-methylphenyl, etc. The
preferred R' groups may be hydrogen or lower alkyl, i.e. C.sub.1
-C.sub.10 alkyl, groups including eg methyl, ethyl, n-propyl,
i-propyl, butyls, amyls, hexyls, octyls, decyls, etc. R' may
preferably be hydrogen.
R" may be a hydrocarbon selected from the same group as R' subject
to the fact that R" is divalent and contains one less hydrogen.
Preferably R' is hydrogen and R" is --CH.sub.2 CH.sub.2. Typical
amines which may be employed may include those listed below in
Table I.
TABLE I
propylenediamine (PDA)
diethylenetriamine (DETA)
triethylenetetramine (TETA)
tetraethylenepentamine (TEPA)
pentaethylenehexamine (PEHA)
The preferred amine may be tetraethylenepentamine.
The charge aldehyde which may be employed may include those
preferably characterized by the formula R.sup.2 CHO.
In the above compound, R.sup.2 may be hydrogen or a hydrocarbon
group selected from the group consisting of alkyl, aralkyl,
cycloalkyl, aryl, alkaryl, alkenyl, and alkynyl including such
radicals when inertly substituted. When R.sup.2 is alkyl, it may
typically be methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl,
sec-butyl, amyl, octyl, decyl, octadecyl, etc. When R.sup.2 is
aralkyl, it may typically be benzyl, beta-phenylethyl, etc. When
R.sup.2 is cycloalkyl, it may typically be cyclohexyl, cycloheptyl,
cyclooctyl 2-methylcyclo-heptyl, 3-butylcyclohexyl,
3-methylcyclohexyl, etc. When R.sup.2 is aryl, it may typically be
phenyl, naphthyl, etc. When R.sup.2 is alkaryl, it may typically be
tolyl, xylyl, etc. When R.sup.2 is alkenyl, it may typically be
vinyl, allyl, 1-butenyl, etc. When R.sup.2 is alkynyl, it may
typically be ethynyl, propynyl, butynyl, etc. R.sup.2 may inertly
substituted i.e. it may bear a non-reactive substituent such as
alkyl, aryl, cycloalkyl, ether, halogen, nitro, etc. Typically
inertly substituted R groups may include 3-chloropropyl,
2-ethoxyethyl, carboethyoxymethyl, 4-methyl cyclohexyl,
p-chlorophenyl, p-chlorbenzyl, 3-chloro-5-methylphenyl, etc. The
preferred R.sup. 2 groups may be lower alkyl, i.e. C.sub.1
-C.sub.10 alkyl, groups including eg methyl, ethyl, n-propyl,
i-propyl, butyls, amyls, hexyls, octyls, decyls, etc. R.sup.2 may
preferably be hydrogen.
Typical aldehydes which may be employed may include those listed
below in Table II.
TABLE II
formaldehyde
ethanal
propanal
butanal etc.
The preferred aldehyde may be formaldehyde employed as its
polymer-paraformaldehyde.
The charge phenols which may be employed in practice of the process
of this invention may preferably be characterized by the formula
HR.sup.3 OH. It is a feature of these phenols that they contain an
active hydrogen which will be the site for substitution.
Poly-phenols (eg compounds containing more than one hydroxy group
in the molecule whether on the same ring or not) may be employed.
The rings on which the hydroxy groups are sited may bear inert
substituents. However, at least two positions, e.g., ortho- and
para-, to a phenol hydroxy group, must be occupied by an active
hydrogen as this is the point of reaction with the iminium salt
group.
R.sup.3 may be an arylene group typified by --C.sub.6 H.sub.4 --,
--C.sub.6 H.sub.3 (CH.sub.3)--, or --C.sub.6 H.sub.3 (C.sub.2
H.sub.5)--.
Typical phenols which may be employed may include those listed
below in Table III.
TABLE III
Phenol
Bisphenol A
Resorcinol
Mono-nonyl phenol
Beta-naphthol
The preferred phenols may be phenol or mono-nonyl phenol.
In practice of the process of this invention, the reagents are step
wise reacted with a succinic acid anhydride bearing a polyolefin
substituent containing residual unsaturation in a "one pot
reaction".
The succinic acid anhydride may be characterized by the following
formula ##STR2##
In the above formula, R may be a residue (containing residual
unsaturation) from a polyolefin which was reacted with maleic acid
anhydride to form the alkenyl succinic acid anhydride. R may have a
molecular weight M.sub.n ranging from about 500 to about 2000,
preferably about 1000 to about 1300, and more preferably about
1300.
The Mannich phenol coupled glycamide bis-alkenyl succinimide is
prepared by the following sequence of steps in a single flask
preparation as shown below in Scheme I. The first step of the
reaction sequence involves reacting a polyethyleneamine with an
alkenyl succinic acid anhydride (ASAA), respectively, in a 1:2
molar ratio to form the bis-alkenyl succinimide (A) intermediate.
To this intermediate (A) is added enough glycolic acid to acylate
all of the free basic amines except for one or one equivalent amine
to form the partially glycolated bis-alkenyl succinimide (B). To
this succinimide (B) is added an excess of paraformaldehyde to form
the iminium salt of the glycolated bis-alkenyl succinimide (C).
Immediately after the addition of formaldehyde (3 min) is added one
half of an equivalent of phenol relative to the
polyethylenediamine, or any other phenolic compound capable of
reacting with a iminium salt twice, to give the derived product of
Mannich phenol coupled glycamide bis-alkenyl succinimide (D).
The product so obtained may be a 50-80, say 50 wt.% solution of the
desired additive in inert diluent; and preferably it is used in
this form. ##STR3##
The preferred acylating agents which are carboxylic acids may be
glycolic acid; oxalic acid; lactic acid; 2-hydroxymethyl propionic
acid, or 2,2-bis(hydroxymethyl)propionic acid. The most preferred
being glycolic acid.
Acetylation may be effected preferably by addition of the
acetylating agent (e.g., glycolic acid or oxalic acid) to the
reaction product of the polyethyleneamine and the succinic acid
anhydride.
Acylation is preferably effected by adding the acylating agent
(typically oxalic acid or glycolic acid) in an amount of about 0.5
to about 3.0 equivalents per mole of active amine employed.
For example, when tetraethylenepentamine (TEPA) is employed, there
are 1.7 equivalents of glycolic acid added. Similarly, when
triethylenetetramine (TETA) is used, about 0.7 equivalent of
glycolic acid is added; and when pentaethylenehexamine (PEHA) is
employed, about 2.7 equivalents of glycolic acid are added to the
reaction.
During acylation, the carboxyl group of the acylating agent bonds
to a nitrogen atom to form an amide. Acylation is carried out at
100.degree. C.-180.degree. C., say 160.degree. C. for 2-24 hours,
say 8 hours preferably in the presence of an excess of inert
diluent-solvent.
The partially acylated product may in one of its embodiments be
represented by the formula ##STR4## wherein R is
polyisobutylene.
In order to illustrate the effectiveness of the present compounds,
i.e., coupled glycolated succinimides, as dispersants with viton
seal compatibility, there are several tests to which the present
succinimides have been subjected. These tests include the Bench VC
and VD Tests, the Bench Sequence VD Test, the Caterpillar I-G2
Engine Test, and the Daimler-Benz Viton Compatibility Test. These
tests are described below in more detail as well as the results of
the various tests are provided below in Tables IV, V, VI, and
VII.
THE BENCH VC TEST (BVCT)
This test is conducted by heating the test oil mixed with a
synthetic hydrocarbon blowby and a diluent oil at a fixed
temperature for a fixed time period. After heating, the turbidity
of the resulting mixture is measured. A low percentage turbidity (0
to 10) is indicative of good dispersancy while a high value (20 to
100) is indicative of an oil's increasingly poor dispersancy. The
results obtained with the known and present dispersants are set
forth in Table IV below at 6 and 4 percent by weight concentration
respectively, in an SAE 10W-40 fully formulated motor oil.
THE BENCH VD TEST (BVDT)
In the Bench VD Test, (BVDT), oil samples are artificially degraded
by bubbling air for six hours through a mixture of test oil and
synthetic blowby at 290.degree. F. Every hour, synthetic blowby is
added and at the 5th and 6th hour of the test, samples are removed
and diluted with SNO-7/20 diluent oil and their turbidity measured.
Low turbidity in the BVDT indicates good lubricant dispersancy as
related to the Sequence VD Test. The Sequench VD engine correlation
work predicts that SF (i.e. satisfactory) quality lubricants should
read 60 or less in the BVDT (turbidity units); oils 70 or greater
would be predicted to do significantly poorer in the Sequence VD
Test.
Reference standard: The reference oil standard used in this test
has had an average Sequence VD deposit rating of 6.81=Average
varnish, 9.56=Average sludge. In the BVDT the 6 hour turbidity
should be 55+/-12. The reference oil is included in each BVDT run.
The resultant BVDT runs are provided below in Table IV.
TABLE IV ______________________________________ Bench VC.sup.1 and
Bench VD.sup.2 Test Results of Phenolic COUPLED GBSD.sup.3 TYPE
DISPERSANTS.sup.4 DISPERSANT BVCT.sup.5,6 BVDT.sup.5
______________________________________ 1 GBSD (TEPA, H-300 ASAA) --
101, 104 2 GBSD (TEPA, H-300 ASAA, 25/33 41 phenol) 3 GBSD (TEPA,
H-300 ASAA, 8/11 21 resorcinol) 4 GBSD (TEPA, H-300 ASAA, 9/12 59
bisphenol A) 5 GBSD (TEPA, H-300 ASAA, 10/12 17 thiodiphenol) 6
GBSD (TEPA, H-300 ASAA, 8/11 162, 120 2,6-dimethylphenol) 7 GBSD
(TEPA, H-300 ASAA, 11/11 69, 178 2,6 di-t-butylphenol) 8 Modified
GBSD (PEHA, H-300 ASAA, 8/6 54 phenol) 9 Modified GBSD (PEHA, H-300
ASAA, 9/6 36 nonyl phenol) 10 GBSD (PEHA, H-300 ASAA, phenol 12/15
24 11 GBSD (PEHA, H-100 ASAA, phenol 23/15 36 12 GBSD (PEHA, H-50
ASAA, phenol -- -- ______________________________________ .sup.1
Bench Test for sludge dispersancy performance. .sup.2 Bench Test
for varnish dispersancy performance. .sup.3 GBSD is a Glycamide
bissuccinimide dispersant (90% bis and 10% mono). .sup.4 These
phenolic coupled dispersants were blended at 7.4 wt. % in an SAE 30
SF/CD motor oil. .sup.5 The lower the value, the better is
dispersancy. .sup.6 The number to the right of the slash mark
represents GBSD used as the good reference. TEPA
Tetraethylenepentamine. PEHA Pentaethylenehexamine. ASAA Alkenyl
succinic acid anhydride; H50 ASAA (mw.apprxeq.750); H100 ASAA
(mw.apprxeq.1000); H300 ASAA (mw.apprxeq.1300).
SEQUENCE VD TEST
Various dispersants including known dispersant and the present
dispersants were tested by the Sequence VD gasoline engine test in
a fully formulated oil motor at about 5.7 wt.% and gave the results
shown below in Table V.
The Sequence VD test evaluate the performance of engine oils in
terms of the protection provided against sludge and varnish
deposits as well as valve train wear. The test was carried out with
a Ford 2.3 liter 4 cylinder gasoline engine using cyclic low and
mid range engine operating temperatures and a high rate of
blowby.
TABLE V ______________________________________ SEQUENCE VD
TESTING.sup.1 Treatment Levels
______________________________________ Dispersants (wt. %) Modified
GBSD.sup.2 6.1 -- -- (N-300 ASAA, PEHA) Modified GBSD -- 5.7 --
(N-300 ASAA, PEHA, phenol/CH.sub.2 O) Modified GBSD -- -- 5.5
(N-300 ASAA, PEHA nonyl phenol/CH.sub.2 O) Sequence VD Average
Sludge 9.42 9.67 9.6 Average Varnish 5.01 6.40 6.1 Piston Skirt
Varnish 6.82 7.00 7.0 (The higher the values, the better the
performance) ______________________________________ .sup.1 These
dispersant were evaluated in a SAE 30 grade SF/CD motor oil
formulation. .sup.2 GBSD is a Glycamide bissuccinimide dispersant
(90% bis and 10% mono.) TEPA Tetraethylenepentamine PEHA
Pentaethylenehexamine ASAA Alkenyl succinic acid anhydride; H100
ASAA (mw.apprxeq.1000); H300 ASAA (mw.apprxeq.1300).
THE CATERPILLER 1-G2 TEST
The diesel engine performance of Example II, as measured by the
Caterpiller 1-G2 testing in SAE 30 fully formulated oil formulation
using 0.055 wt.% nitrogen from the dispersant gave the results
shown below in Table VI.
TABLE VI ______________________________________ Caterpillar 1-G2
Engine Testing.sup.1 ______________________________________
Dispersant, wt. % GBSD.sup.2 6.32 -- -- GBSD (PEHA, H-300 -- 6.32
-- ASAA, Mannich phenol) GBSD (PEHA, H-300 -- -- 6.32 ASAA, Mannich
nonyl phenol) Cat. 1-G2 120 hrs TGF (%) 63 61 -- WTD 200 156 -- 480
hrs TGF (%) 80 66 76 WTD 208 220 292
______________________________________ .sup.1 These dispersants
were evaluated in a prototype SAE 30 SF/CD motor oil formulation.
.sup.2 GBSD is a Glycamide bissuccinimide dispersant (90% bis and
10% mono). PEHA Pentaethylenehexamine ASAA Alkenyl succinic acid
anhydride; H100 ASAA (mw 1000); H300 ASAA (mw 1300). TGF Top grove
fill. WTD Weighted total demerits.
THE DAIMLER-BENZ VITON COMPATIBILITY TEST
An important property of a lubricating oil additive and a blended
lubricating oil composition containing additives is the
compatibility of the oil composition with the rubber seals employed
in the engine. Nitrogen-containing succinimide dispersants employed
in crankcase lubricating oil compositions have the effect of
seriously degrading the rubber seals in internal combustion
engines. In particular, such dispersants are known to attack Viton
AK-6 rubber seals which are commonly employed in internal
combustion engines. This deterioration exhibits itself by sharply
degrading the flexibility of the seals and in increasing their
hardness. This is such a critical problem that the Daimler-Benz
Corporation requires that all crankcase lubricating oils must pass
a Viton Seal Compatibility Test before the oil compostion will be
rated acceptable for engine crankcase service. The AK-6 Bend Test
is described below and is designed to test the Viton seal
compatibility for a crankcase lubricating oil composition
containing a nitrogen-containing dispersant.
The AK-6 Bend Test is conducted by soaking a sample of Viton AK-6
rubber at an elevated temperature in the oil being tested then
determining the bending properties and hardness of the Viton rubber
sample against a suitable sample. Specifically, a 38 by 9.5 mm slab
of a Viton AK-6 rubber cut with the grain of the rubber is placed
in a 30 ml wide-mouth bottle with 20 ml of the test oil. The bottle
is sealed and the test sample placed in an oven at 149.degree. C.
for 96 hours. The bottle is removed from the oven and the rubber
specimen taken from the initial bottle and placed into a second
bottle with a new charge of test oil. After 30 minutes in the new
oil charge, the rubber specimen is removed from the second bottle
and submitted to a Bend Test. This is done by bending the rubber
specimen 180.degree.. The degree of cracking is observed and
reported as follows: no cracking (NC) surface cracking (SC) or
cracking (C). If cracking is observed, the test is terminated on
that particular sample.
If no cracking has been observed, the rubber specimen is returned
to the bottle containing the second oil charge and this bottle is
returned to the oven maintained 149.degree. C., the bottle is
removed from the oven and the rubber specimens withdrawn and placed
into another bottle containing a fresh oil charge for 30 minutes,
following which the bend test is repeated.
If the rubber specimen continues to pass the bend test, the test is
continued for 2 more heat-soak cycles of 96 hours and 72 hours
respectively, each heat-soak cycle being followed by the bend test
for total test time of 336 hours from the time the specimens were
initially put into the oven.
Following the above procedure, each rubber specimen is removed from
its bottle, washed in naphtha to remove all oil traces and then air
dried. The rubber specimens are then submitted to a hardness test
according to the procedure described in ASTM D2240 following which
a final bend test is made on all specimens.
The results of the Daimler-Benz test runs are provided below in
Table VII.
TABLE VII ______________________________________ Daimler-Benz Viton
Compatibility Test.sup.1 Tensile Dispersant.sup.2 Cracking %
Elongation Strength ______________________________________
GBSD.sup.3 (H-300, None 166 9.0 ASAA Mannich phenol) n/mm.sup.2
GBSD (H-300, ASAA None 166 9.0 Mannich bisphenol A) GBSD (H-100
ASAA None 154 8.4 Mannich phenol) GBSD (H-50 ASAA, None 133 6.7
Mannich phenol) Good Reference Sample None 130 7.5
______________________________________ .sup.1 All dispersants were
evaluated in a single grade SAE 30 SF/CD moto oil formulation at
6.3 wt. %. .sup.2 All dispersants were prepared using PEHA
(Pentaethylene hexamine a the amine source). .sup.3 GBSD is a
Glycamide bissuccinimide dispersant (90% bis and 10% mono). ASAA
Alkenyl succinic acid anhydride; H50 ASAA (mw.apprxeq.750); H100
ASAA (mw.apprxeq.1000); H300 ASAA (mw.apprxeq.1300). n/mm.sup.2
newton/millimeter.sup.2
* * * * *